Analysis of chemical substances by liwenting

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									Analysis of chemical substances in
balloons


Nils Nilsson
Danish Technological Institute




Survey of Chemical Substances in Consumer
Products, No. 89 2007
The Danish Environmental Protection Agency will, when opportunity
offers, publish reports and contributions relating to environmental
research and development projects financed via the Danish EPA.


Please note that publication does not signify that the contents of the
reports necessarily reflect the views of the Danish EPA.


The reports are, however, published because the Danish EPA finds that
the studies represent a valuable contribution to the debate on
environmental policy in Denmark.
Contents


PREFACE                                                          5

SUMMARY AND CONCLUSION                                           7

1     INTRODUCTION                                               9
    1.1    NITROSAMINE FORMATION                                 9
    1.2    LEGISLATION/ RECOMMENDATIONS ON LIMIT VALUES FOR
           NITROSAMINES AND NITROSATABLE SUBSTANCES IN BALLOONS
           BASED ON LABORATORY ANALYSES, ETC.                   10
2     ANALYSIS OF BALLOONS ON THE MARKET                        13

3     PURCHASED BALLOONS                                        15

4     SELECTION OF BALLOONS FOR ANALYSIS                        17

5     SCREENING ANALYSIS BY TLC                                 19
    5.1    SAMPLE PREPARATION AND METHOD OF ANALYSIS            19
      5.1.1   Introduction                                      19
      5.1.2   Sample preparation                                19
      5.1.3   The TLC-analysis                                  19
      5.1.4   Results from the TLC-screenings                   20
6     SUPPLEMENTARY IDENTIFICATION BY
      GC/MS-HEADSPACE ANALYSIS                                  23
    6.1    VERIFICATION BY GC/MS-HEADSPACE ANALYSIS AT 150 ºC   23
      6.1.1   Introduction                                      23
      6.1.2   Method                                            23
      6.1.3   Results from the verification analysis            23
    6.2    HEADSPACE ANALYSIS AT 80 ºC                          25
7     ANALYSIS FOR NITROSAMINES AND NITROSATABLE
      SUBSTANCES                                                27

8     ANALYSIS FOR BIOAVAILABLE HEAVY METALS                    31

9     CONCLUSION IN SHORT                                       33

10        REFERENCES                                            35




                                                                3
4
Preface

The project ”Analysis of chemical substances in balloons” has been carried
out by Danish Technological Institute in the period from mid March 2006 to
mid November 2006.

The project has been headed by project manager lic.scient. Nils H. Nilsson,
Materials Division, who has also been the responsible contact person to the
Environmental Protection Agency (EPA).

The contact persons at EPA were Peter Hammer Soerensen and Frank
Jensen.

The purpose of the present project was to investigate whether balloons
contain or liberate any chemical substances hazardous to health. Principal
focus has been on nitrosamines, nitrosatable substances or other
degradation/conversion products formed from accelerators and other rubber
chemicals used.




                                                                              5
6
Summary and conclusion

For this study 20 different packs of balloons have been purchased at different
retailers. The balloons normally come in different colours and the various
brands differ in size and geometry.

During the purchasing phase we went to a number of supermarkets and the
general impression was that the Danish balloon market is limited to a few
wholesalers, supplying the same products to different supermarkets and
therefore our purchases were confined to only three supermarkets. Other
types of shops have also been included in our analysis but still the general
impression is that only a few wholesalers/manufacturers are dominating the
Danish balloon market.

As balloons are dangerous toys for children less than 8 years labelling
regulations are laid down in the Toys Act 88/378/EEC. According to the
standard in the Toys Act, EN 71-1, the balloons shall to in order comply with
the CE-standard be provided with warning labels saying that children under 8
years should be supervised and that defective balloons or parts hereof shall be
discarded. A further requirement is that the balloons made of natural latex
shall be marked ”contain natural rubber latex”.

The labelling of the purchased balloons differs a lot. Most of them are
however CE labelled and most of the packaging had warning labels about use
by children under 8 years. Further, the packaging often advised caution with
children less than 3 years. In some cases the warnings were not in Danish and
some of the balloons had inadequate labelling.

The majority of the balloons are made of natural latex, but more of them had
no informative label about this.

Twelve of the purchased balloons have been screened by thin layer
chromatography (TLC) in order to determine the accelerator types used by
vulcanisation.

On basis of these screenings and the amount of extracted substance four
balloons were selected for analysis for nitrosamines and nitrosatable
substances according to DS/EN 12868, ”Child Care Articles: Methods for
determination of the release of N-nitrosamines and N-nitrosatable substances
from bottle teats and soothers of elastomers or rubber”. Likewise, analyses
have been made on release of volatile substances from balloons at 80 ºC.
Further, three balloons were selected for test of bioavailable heavy metals
according to EN 71-3 ”Safety of Toys - Migration of certain elements.

The result was that there was no measurable release of heavy metal, but all the
balloons gave off nitrosamines in concentrations higher than allowed for
soothers and bottle teats. Surprisingly, the release of nitrosatable substances
was generally in very high concentrations. In two cases the contents was so
high that the standardised method could not completely convert those of the
amines, which were highest in concentration, within the reaction time for
conversion to nitrosamines. It is therefore assessed that this method provides



                                                                               7
    too low results for nitrosatable substances at high amine concentrations. Not
    unexpectedly, the most frequent nitrosatable amine is dibutylamine, which is
    often present as accelerator in vulcanised latex products in the form of the
    zinc salt of dibutyldithiocarbamic acid. Second comes the zinc salt of
    dimethyldithiocarbamate, which is often applied in combination with the zinc
    salt of dibutyldithiocarbamatic acid.

    Germany has laid down limit values for release of nitrosamines and
    nitrosatable substances from balloons.

    The analysed balloons all complied with the limit value of 0.2 mg/kg for
    migration of nitrosamines according to DS/EN 12868, but only one of the
    four analysed balloons complied with the requirement to nitrosatable
    substances of 2 mg/kg. This balloon type bore the TÜV quality mark.

    At 150 ºC a headspace GC/MS analysis was made of the volatile substances
    formed by decomposition of rubber chemicals. A wide range of different
    degradation products are formed from the chemical substances in the
    balloons. This analysis has been used to confirm the results from the TLC
    screening.

    The analysis established evaporation of several hazardous organic substances
    from a balloon purchased in a discount store. The other three balloon types
    showed no degassing of these chemical substances.

    A headspace analysis at 80 ºC of the balloons demonstrated liberation of
    carbon disulfide from the four analysed balloons. The balloon from the
    discount store also liberated dibutylamine and BHT (antioxidant).




8
1 Introduction

Balloons are popular toys among children and the market offers a variety of
different balloons. Even though balloons are not recommended for children
under three years it is most likely that children of that age will get in contact
with balloons.

Almost all the balloons are made of natural latex.

Special focus is on the release of nitrosamines from balloons as several studies
have shown that carcinogenic nitrosamines are given off in migration tests to
artificial saliva. The nitrosamines are formed from secondary amines liberated
from the accelerators used.

Other substances might be harmful to the health, i.a. problematical such as
thiuram accelerators and mercaptobenzothiazole (MBT), which may cause
type IV-allergy.

Balloons are dyed in different colours and therefore colorants may also
present a risk.

Finally it is a well-known fact that for a small part of the population the
proteins in natural latex may cause type I-allergy, which may be life
threatening.

This aspect will not be studied in detail in this limited project, but it should be
added that especially by bursting of balloons there is a risk of affecting the
proteins if the balloons are powdered with corn starch or other release agents
(talc) which are added to the finished product in order to reduce the tackiness
of the rubber.

Natural rubber is extracted from the tree Hevea Brasiliensis, where the rubber
latex is drained from the cortex in the form of latex.

The latex is stabilised with ammonia to avoid coagulation. Immediately after
dispersing of rubber chemicals the latex can be used for production of
balloons or other dipped products (e.g. bottle teats, gloves and condoms). A
prevulcanisation will often take place when heating the latex solution to 60-70
°C for a shorter period (approx. 6 hours). The latex used for balloons
normally has a dry matter content of 60 % w/w.


1.1 Nitrosamine formation

Nitrosamines can be formed oxidatively from the amines that can be liberated
from the applied thiuram-ultra accelerators during vulcanisation of the natural
latex.

The most common accelerators for dipped latex products are the following:
   • Zink dimethyl dithiocarbamate          ZDMC
   • Zink diethyl dithiocarbamate           ZDC



                                                                                    9
         •   Zink di-n-butyl dithiocarbamate          ZDB
         •   Zink ethylphenyl dithiocarbamate         ZEPC
         •   Zink dibenzyl dithiocarbamate            ZBED
         •   Zink pentamethylene dithiocarbamate      ZPD

     The most frequently applied accelerators are salts of dithiocarbamic acid in
     the form of zinc dimethyldithiocarbamate, zinc dimethyldithiocarbamate and
     zinc di-n-butyldithiocarbamate in the order given.

     By vulcanisation carbon disulfide will be formed during the release of the
     secondary amines, which are part of the chemical building blocks for the
     accelerators:

         •   Dimethylamine
         •   Diethylamine
         •   Di-n-butylamine
         •   Diethylphenylamine
         •   Dibenzylamine

     In the presence of nitrosatable substances (NOX) all five secondary amines
     can form nitrosamines.

     Due to the low vapour pressure the nitrosamine from dibenzyl amine is
     considered to be relatively unproblematic in health terms, but is still one of the
     nitrosamines to be quantified according to DS/EN 12868.

     Nitrosamines may also be formed from other accelerators or sulphur donors,
     which might be ingredients in the latex recipe, e.g. dimethylthiuram mono-
     and disulfide, diethylthiuram mono- and disulfide as well as 4,4´-
     dithiomorpholine.

     2-Morpholino-benzothiazole sulfenamide is a sulphenamide accelerator,
     which may cause formation of N-nitroso-morpholine.

     MBT is a mercaptothiazole accelerator, known as a medium strong
     accelerator, and which is also being used as accelerator in natural rubber latex.

     It is used by dipped products together with ultra accelerators of the
     thiocarbamate or the thiuram type to provide improved process safety.
     Further, MBT is being used within production of technical rubber products
     as it is one of a few accelerator types which do not give off nitrosamines
     during vulcanisation.


     1.2 Legislation/ recommendations on limit values for nitrosamines
     and nitrosatable substances in balloons based on laboratory analyses,
     etc.


     There is, however, no actual legislation for balloons as is the case for e.g. teats
     for soothers and feeding bottles. However, balloons, which are marketed and
     sold in Germany must comply with the German limit values laid down for
     consumer products according to BgVV recommendation XXI.




10
Based on exposure scenarios the BfR ”Bewertung von Nitrosaminen in
Luftballons” (ref. 4) has laid down a maximum liberation of nitrosamines
from balloons of 0.2 mg/kg and 2 mg/kg for nitrosatable substances.

EU directive 93/11/EEC stipulates that rubber teats and soothers may not
release nitrosamines and nitrosatable substances in amounts larger than 10 µg
per kg rubber for nitrosamines and 100 µg per kg rubber for nitrosatable
substances for artificial saliva (DS/EN 12868). In the USA the limit value by a
dichlormethane extraction of 20 µg per kg for soothers and 10 µg per kg for
rubber teats.


A German investigation has shown that for approx. 81% of the investigated
balloons in 2001, the release of nitrosamines and nitrosatable substances
(nitrosamine precursors) for artificial saliva according to EN 12 868 (1 hour
at 40 ºC) was higher than the limit values applying for soothers and rubber
teats.

An analysis in 2003 of 14 balloons established that only one of these complied
with the limit value of less than 10 µg per kg for nitrosamines.

The nitrosamines found in the investigation were N-dimethylnitrosamine (97
% of the balloons), N-dibutylnitrosamine (93 % of the balloons) and
diethylnitrosamine (34 % of the balloons). In 9 % of the balloons was found
N-nitrosomorpholine.

It is not surprising to find the three first-mentioned types of nitrosamines, as
the most frequently used accelerators in natural latex will be capable of
forming these nitrosamines. The presence of N-nitrosomorpholine in 9 %
indicates that morpholine derivates are being used either as sulphur donor or
as accelerator (sulfenamide types).

According to ref. 3 the European industry has responded to the proposed
amendment to the Toys Directive concerning nitrosamines in balloons, that
the industry is aware of the risk, but that there is presently no available
technology for complete elimination of the nitrosamines. It is further stated
that a possible total ban on nitrosamines in balloons will fall notably hard on
the European balloon industry and in the worst case it completely close the
industry.




                                                                              11
12
2 Analysis of balloons on the market

The analysis of the balloon market is based on visits to different types of
shops.

The purpose of the analysis is to reveal which balloon brands are being sold to
the consumers.

The following shop types were visited:

   •   Toy stores
   •   Fun items shops
   •   Supermarkets
   •   One department store
   •   One bookshop
   •   One discount shop

Further, we have had contact to a local Danish balloon manufacturer.

Two copies of each balloon type on the market were purchased and one copy
was sent to EPA.

At this initial phase information was retrieved from wholesalers and
manufacturers about the accelerators they had used and whether the balloons
had certificates regarding any regulatory compliance.

DTI has previously experienced that it is rather difficult to gather information
about substances in consumer products – in particular from the Far East
where the majority of the balloon types are produced.

Contacts to importers or distributors confirm this, as the general picture is
that when it comes to the chemical composition of the balloon latex, there are
no records on the accelerators or the other chemicals added to the balloons.

The link to the balloon manufacturer in the Far East may be through a
European wholesaler/buyer in another EU country, for instance Germany.




                                                                              13
14
3 Purchased balloons

In total 20 different balloons have been provided for the project. The balloons
were purchased in toy stores, supermarkets, a department store, a bookshop,
a fun items shop and in a discount store. Records were made on the data on
the packaging as to CE labelling, warnings about use and other consumer
information. The records appear from Table 3.1.
Table 3.1 Purchased balloons
Product Shop type        Consumer information                        Comment
nr.
1          Toys shop     CE labelled, warning < 8 years (i.a. in     Balloon figures in different
                         Danish).                                    colours (40 pcs.)
                         Not for 0-3 years , contains small
                         parts. Natural latex
2          Toy store     CE labelled, warning, not for children      Funny face balloons (6 pcs.)
                         under 8 years. Warning symbol 0-8
                         years
3          Toy store     CE labelled, warning in Danish, not         Ass. balloons in different
                         for children under 8 years. Warning         colours (20 pcs.)
                         symbol 0-8 years, natural latex,
                         balloon pump recommended
4          Toy store     CE labelled, warning in Danish, not         Modelling balloons with
                         for children under 8 years. Warning         pump. Different colours (15
                         symbol 0-8 years, natural latex,            pcs.)
                         balloon pump recommended.
5          Toy store     CE labelled, warning < 8 years (i.a. in     Red, yellow, and green (3
                         Danish).                                    pcs.)
                         Not recommended for 0-3 years,
                         natural latex, balloon pump
                         recommended
6          Toy store     CE labelled, warning < 8 years (i.a. in     Metallised balloons (8 pcs.)
                         Danish).
                         Not recommended for 0-3 years,
                         natural latex, balloon pump
                         recommended
7          Toy store     CE labelled, warning < 8 years (i.a. in     Metal balloons in red and
                         Danish).                                    white (10 pcs.)
                         Not recommended for 0-3 years,
                         natural latex, balloon pump
                         recommended
8          Supermarket   CE labelled, warning < 8 years (i.a. in     Metal balloons in blue, grey
                         Danish).                                    and green (8 pcs.)
                         Not recommended for 0-8 years
                         warning symbol, natural latex,
9          Supermarket   Not CE labelled. Caution: Not               Pink and mauve balloon (2
                         recommended for children less than          pcs.). Probably in natural
                         three years                                 latex, but not labelled
10         Supermarket   CE labelled, warning < 8 years (i.a. in     Balloons in four colours (8
                         Danish).                                    pcs.). It is stated that it is
                         Not recommended for 0-8 years,              based on natural latex,
                         warning symbol                              however, not in Danish
11         Toy store     CE labelled, warning text not for < 8       Balloons in three colours (6
                         years, but not in Danish, warning           pcs.). Probably in natural
                         symbol > 0-8 years                          latex, but not labelled as
                                                                     such
12        Department       CE labelled, warning < 8 years (i.a. in   Balloon figures in different
          store            Danish)                                   colours (10 pcs.)
                           Not for 0-8 years warning symbol,
                           Natural latex,
13        Department       CE labelled, warning in text, for         Balloons in different colours
          store            children under 8 years                    (50 pcs.), probably in natural




                                                                                                  15
     Product   Shop type     Consumer information                      Comment
     nr.
                                                                       latex, but not labelled
     14        Supermarket   CE labelled, warning i.a. in Danish for   Balloons in different colours
                             children under 8 years, no warning        (50 pcs.), probably in natural
                             symbol                                    latex, but not labelled
     15        Fun items     Not CE labelled, warning symbol for       Balloons in different colours
               shop          0-3 years. Warning for children less      (13 pcs.)
                             than 8 years i.a. in Danish, Do not put
                             in mouth. To be inflated only with
                             balloon pump.
     16        Discount      CE labelled, warning sign 0-3 plus text   Red balloons. probably in
               store         – not recommended for children            natural latex, but not labelled
                             under three years
     17        Bookshop      Not CE labelled, but texted not for       Round balloons in white and
                             children under 3 years                    red (10 pcs.). Probably in
                                                                       natural latex, but not
                                                                       labelled.
     18        toy store     CE labelled, texted not for children      Self-inflatable metallised
                             under 3 years, contains particles         balloon (1 pc.). Hardly
                                                                       natural latex-based
     19        Supermarket   CE labelled, warning < 8 years(not in     Blue, yellow, red (6 pcs.)
                             Danish)
                             Not for 0-3 years, Tüv Q-label
     20        Supermarket   CE labelled, warning < 8 years (not in    Orange, yellow, red (6 pcs.)
                             Danish)
                             Not for 0-3 years, Tüv Q-certificate




16
4 Selection of balloons for analysis

Twelve balloons were chosen for an initial screening for accelerators by thin
layer chromatography (TLC). The following were selected:

Balloons numbered 1, 3, 6, 8, 10, 11, 13, 14, 15, 16, 17, and 20.

The priority criteria were:

    •   The balloons must be made of or presumedly made of natural rubber
        latex
    •   The selected balloons must represent manufacturers from Denmark
        and abroad
    •   Both discount and luxury balloons should be tested
    •   Balloons with special appeal to children under 8 years

Based on results from the TLC-screenings 4 different balloons were selected
for analysis for nitrosamines and nitrosatable substances according to analysis
method DS/EN 12868 ”Children Care Articles. Methods for determining the
release of N-nitrosamines and N-nitrosatable substances from elastomers or
                              st
rubber teats and soothers”, 1 edition 2000-01-21.

Following were chosen based on the TLC-results and extraction yields for
dichlormethane as solvent: Balloons nos. 3, 6, 16, and 20.

Additionally three types of balloons were selected for heavy metal analysis
according to DS/EN 71-3 ”Toys Safety Regulations – Part 3: Migration of
certain elements”.

Following samples were chosen: Balloon no. 10 yellow, no. 16 red and no. 20
orange.

The choice was made from the following criteria:
   • Orange, yellow and red colours may be cadmium-based
   • One of the balloon types is a discount product and does not comply
      with the requirements to CE-labelling, although it had a CE label.
   • One of the products had famous comic strip figures and had TÜV-
      quality mark.

Additionally four balloon types were selected for GC/MS-screening for
liberated chemical substances from the accelerators according to the methods
previously used by DTI at consumer products analyses. The selection is the
same as for the analysis for nitrosamines and nitrosatable substances, i.e.
balloons nos. 3, 6, 16 and 20. The analyses have been carried out at a
headspace of 80 ºC and 150 ºC, respectively.




                                                                              17
18
5 Screening analysis by TLC


5.1 Sample preparation and method of analysis

5.1.1 Introduction

Thin layer chromatography (TLC) is a preferred chromatographic method
for determination of the accelerators used by vulcanisation of rubber, cured as
well as uncured. Methods for determination of the applied accelerators are i.a.
standardised in ISO 10398 ”Rubber – Identification of accelerators in cured
and uncured compounds” (1998) and ”Kunststoffe im Lebensmittelverkehr”
XXI BII, 2.5.

An important reason for using TLC for analysis of accelerators in rubber is
that the accelerators are being decomposed at higher temperatures and thus
cannot directly be analysed by gas chromatography. Moreover it is common
to use zinc salts of dithiocarbamine acids, which makes the HPLC less
attractive as analysis method. Finally, it is possible to spray TLC plates with
reagents which yield colour according to the applied chemical substance class.

5.1.2 Sample preparation

The extraction of accelerators is made by weighing out 3 g shredded balloon
and extraction with 50 ml dichlormethane 1 hour in ultrasonic bath. The
solvent is decanted and flushed with 25 ml dichlormethane. The procedure is
repeated and the extracts are collected and evaporated. The evaporation
residue is dissolved in 2 ml dichlormethane for the TLC analysis. The amount
of evaporation residue can be seen from the below table.
Table 5.1 Evaporation residue from the dichlormethane extraction
Balloon nr. 1     3    6    8    10   11   13 14 15      16 17     20
%w/w         4.9 4.9 3.2 2.7 4.2 3.0 3.3 3.7 5.0 5.7 2.9           4.0



5.1.3 The TLC-analysis

As developing solvent a mixture of hexane, toluene and methanol in the
proportions 30:58:12 was chosen.

For the visualisation UV-light, 1 % cuprisulphate solution and iodine vapours
were used.

Silica TLC-plates from Merck (Article 1.11798) 20 cm x 20 cm Silica 60 F
254 with concentration zone were used. 5 µl of the concentrated sample
extracts and produces standards were added. The elution of the applied
samples and standard substances took place over a distance of 12 cm from the
start zone.

The reference substances listed in the table were used in concentrations of 1
%. The references were dissolved in dichloromethane, acetone or a mixture of
these.



                                                                            19
     Table 5-2 Reference substances used for for the TLC-screening.
      Reference substance                   Abbr.    CAS nr.
      4,4-Dithiodimorpholine                DTDM 103-34-4
      Dibenzothiazolyl disulfide            MBTS 120-78-5
      2-Mercaptobenzothiazole               MBT      149-30-4
      N-Morpholinyl-2-benzothiozole         MBS      102-77-2
      sulfenamide
      Tetramethyl thiurammonosulfide        TMTM 97-74-5
      Zinc dibenzyl dithiocarbamate         ZBEC     14726-36-4
      Zinc dibutyl dithiocarbamate          ZDBC     136-23-2
      Zinc diethyl dithiocarbamate          ZDEC     14324-55-1
      Zinc dimethyl dithiocarbamate         ZDMC 137-30-4

     5.1.4 Results from the TLC-screenings

     Table 5-3 Survey scheme TLC-screening
     Balloon no.        Result
             1          ZDBC, (ZBEC), ZDMC
             3          ZDBC (ZBEC), ZDMC
             6          ZDBC (ZBEC),ZDMC
             8          ZDBC (ZBEC)
            10          ZDBC (ZBEC)
            11          ZDBC (ZBEC)
            13          ZDBC (ZBEC), ZDMC
            14          ZDBC (ZBEC), ZDMC
            15          ZDBC (ZBEC)
            16          ZDBC (ZBEC)
            17          ZDBC (ZBEC)
            20          ZDBC (ZBEC),ZDMC


     In the chromatographic system it is not possible to differ between zinc salts of
     dibenzyldithiocarbamate (ZBEC) and of dibutyldithiocarbamate ZDBC), as
     they have the same Rf-value (the Rf-value is obtained by dividing the position
     of the substance in the chromatogram by the total possible distance (12 cm).

     The literature (ref.-1) states that it will most likely be ZDBC based on either
     di-n-butylamine or di-isobutylamine.

     According to FDA (Food and Drug Administration, USA) ZDBC may be
     used in amounts of up to 1.5 % in products intended for repeated contact with
     foodstuffs. Similar limits are stated in Kunststoffe im Lebensmittelverkehr, i.e.
     1.2 % for zinc-dialkyldithiocarbamate accelerators.

     The TLC screening cannot with certainty verify the presence of any of the
     other reference substances used at the screening. This applies for 2-MBT and
     MBS and for thiuram mono- and disulfides based on dimethyl-, diethyl- and
     dibutylamine.

     Examples of TLC chromatograms are shown below:




20
Fig. 5.1 TLC of balloon nos. 1, 3, 6, and 8. Visualisation by cupri sulphate




Fig. 5.2 TLC of extract from balloon 1, 3, 6, 8, and 10. Visualisation by iodine vapour




                                                                                          21
     Fig. 5.3 TLC of balloon no.. 20 and a number of reference substances. Visualisation
     iodine.

     There are individual differences in the TLC chromatograms for the selected
     balloons. Partly, colorants were detected in some of them, partly, chemical
     substances were detected with a relatively low Rf-value, and partly a colour
     reaction occurred after the copper sulphate visualisation which seems to
     indicate the presence of a substance with the same value as the zinc salt of
     dimethyldithiocarbamate (balloon nos. 1, 3, and 6), which gives quite another
     colour tone (reddish instead of yellow-green).




22
6 Supplementary identification by
GC/MS-headspace analysis


6.1 Verification by GC/MS-headspace analysis at 150 ºC

6.1.1 Introduction

As there was no unambiguous verification of accelerators by the thin layer
chromatography, a headspace analysis at GC/MS at 150 °C was carried out
on the balloons selected for analysis for nitrosamines and nitrosatable
substances. At this temperature the accelerators will decompose and the
decomposition products can give information about the accelerator types
applied.

6.1.2 Method

The analysis is performed by headspace GC/MS at 150 ºC after one hour’s
exposure. The numerous different chemical substances formed and identified
by the analysis have not been quantified. The relative amount of the chemical
substances has instead been valuated from the area percentages in the
chromatogram.

6.1.3 Results from the verification analysis

The number of organic compounds detected by the GC/MS verification
analysis at 150 ºC appears from Table 6.1.

Table 6.1 Headspace analysis 150 ºC of 4 selected balloons
Balloon no.                                                  3     6       16     20
Chemical substance                              CAS-nr.      Area %
Ethanol                                         64-17-5      -     -       0.58   0.25
Dimethylamine                                  124-40-3      -      0.27   -      -
Acetone                                        67-64-1       4.57   4.35   6.86   4.16
Carbon disulfide                               75-15-0       8.95 20.98 11.25     3.29
2-methylpropenal                               78-84-2       -      0.71   0.85   0.17
Methacroleine                                  78-85-3       3.37   3.07   3.84   3.17
Methylvinylketone                              78-94-4       5.92 4.05     2.44   3.19
Acetic acid                                    64-19-7       -      0.85   -      -
Butanal                                        123-72-8      <1     -      5.44   0.72
2-methylfurane                                 534-22-5      1.84   3.81   4.86   1.69
3-methylbutanal                                590-86-3      -      0.95   1.2    0.27
Benzene                                        71-43-2       -      -      2.44   -
Hydroxyacetone                                 116-09-6      1.65   0.77   -      0.3
Ethylenglycol                                  107-21-1      4.04 14.27    -      1.31
N,N-dimethylthioacetamide                      631-67-4      -      0.31   -      -
Pentanale                                      110-62-3      1.01   -      0.8    -




                                                                                         23
     Balloon no.                                                      3     6       16      20
     Chemical substance                                  CAS-nr.      Area %
     Propoylenglycol                                     57-55-6      1.17 -        -       -
     ?, maybe 3-methyl-1,4-heptadien or 2,4-heptadienal 1603-01-6     4.5    3.08   2.82    3.24
     Pyrrol                                              109-97-7     -      -      0.59    -
     Dimethylcyanamide                                   1467-79-4    0.6    0.46   0.22    -
     Dimethylformamide or 2-butanamine                   68-12-2      2.91   3.52   0.53    0.54
     Ethylacetate                                        141-78-6     1.77   1.11   -       -
     Hexanal                                             66-25-1      1.29   0.94   1.23    0.74
     2-methyl-pyridine + isomers                         109-06-8     -      -      0.61    -
                                                         108-99-6
     Methyl-pyrazine                                     109-08-0     -      -      0.44    -
     2-methylpyrrol                                      636-41-9     0.72 0.39     0.48    0.12
     Chlorobenzene                                       108-90-7     -      -      0.5     -
     N,N-dimethylacetamide                               127-19-5     -      0.91   -       -
     ?, 6,10-dimethyl-5,9-dodecadiene-2-on or similar.   1000132-10-9 1.31   -      -       -
     1-(1-cyclohexen-1-yl)-ethanone                      932-66-1     -      0.39   -       3.19
     5-methyl-3-methylene-5-hexene-2-one                 51756-18-4   4.59 2.82     2.77    -
     ? Cyclic alkane/alkene                                           -      3.98   -       -
     2-hexen-1-ol acetate                                2497-18-9    -      -      1.14    0.73
     N-butyliden-1-butanamine                            4853-56-9    -      -      0.24    -
     ?Might be branched alkene                                        -      -      -       4.41
     3,5,5-trimethylhexanal                              5435-64-3    -      -      -       4.11
     ?, Branched alkanes C10-C15                                      -      -      -       29.1
     Ethylmethylbenzene isomer                           611-14-3                           0.87
                                                         98-82-8
     Dimethyl-pyrazine                                   123-32-0                   0.53
                                                         108-50-9
     Dibutylamine                                        111-92-2                   12.47
     Phenol                                              108-95-2                   0.62
     2-pentylfurane                                      3777-69-3                  0.46
     Aniline                                             62-53-3                    3.36
     ?, Maybe dimethylnitrosamine                        62-75-9      0.83          0.64
     ?, 2-methyl-2-butene-1-ol                           4675-87-0    8.67
     Benzaldehyde                                        100-52-7     2.53   1.33
     Trimethylbenzene                                    108-67-8     0.68
                                                         526-73-8
     ? Maybe 4,4-Dimethyl-1-hexene                       1647-08-1    1.75
     N,N-dimethylthioformamide                           758-16-7     3.27   2.1
     Dihydro-5-ethenyl-5-methyl-2-(3H)-furanone          1073-11-6    8.01 3.85     2.94    5.12
     1-Methyl-3-propylbenzene + isomers                  1074-43-7                          5.18
     Undecane                                            1120-21-4    1.62   0.91   -       10.75
     Methylaniline                                       100-61-8     -      0.66   -       -
                                                         95-53-4
     Acetophenone                                        98-86-2      0.73 -        -       -
     Dodecane                                            112-40-3     0.63 0.26     -       2.75
     1,2,3,4-tetrahydronaphthalene                       119-64-2     -      -      -       0.33
     Dibutylnitrosamine                                  924-16-3     -      -      0.54    -




24
Balloon no.                                                3     6     16       20
Chemical substance                            CAS-nr.      Area %
Benzothiazol                                  95-16-9      2.23 1.23   -        -
N,N-dibutylformamide                          761-65-9     1.03   -    2.95     0.13
BHT                                           128-37-0     0.99 0.34   10.95 0.2
Hexadecene                                    629-73-2     6.43 -      -        -
?, Maybe 3-eicosene                           74685-33-9   0.96 0.56   0.37     -


Total % integrated peaks                                   91     83   88       90


As can be seen from Table 6.1 there are many different substance types, some
originating from the used accelerators, others may be formed from the
colorants. Balloon no. 16 is producing the most different substances in the
headspace, i.a. chlorobenzene, benzene, aniline, and dibutylnitrosamine.
These substances are not liberated in measurable amounts from the other
balloons. Balloon no. 16 was bought in a discount shop.

All samples liberated carbon disulfide, largest amount from balloon no. 6 and
smallest amount from balloon no. 20.

N,N-dibytylformamide was liberated from balloons nos. 3, 16, and 20. It is a
typical degradation product from the zinc salt of dibutyldithiocarbamate.
Balloon no. 16 is also liberating dibutylamine and the corresponding
nitrosocompound. Dimethylamine is released from balloon no. 6 and
dimethylformamide from all four balloons. It is a typical degradation product
from derivates of dimethyldithiocarbamine acid.


6.2 Headspace analysis at 80 ºC

An analysis of the liberated substances in headspace at 80 °C was performed.
At this temperature only a minor decomposition of the added rubber
chemicals will occur. The analysis results appear from Table 6.2.

Table 6.2 Concentration of volatile substances in headspace at 80 C in µg
Chemical            CAS-no.    Balloon       Balloon        Balloon no.       Balloon no.
substance                      no. 3         no. 6          16                20
Carbondisulphide 75-15-0       0.13          2.1            0.61              0.12
Dibutylamine        111-92-2   Not           Not            0.16              Not
                               detected      detected                         detected
BHT                 128-37-0   Not           Not            2.8               Not
                               detected      detected                         detected
1,2-ethandiol       107-21-1   Not           1,2            Not               Not
                               detected                     detected          detected
Hydrocarbons                   Not           Not            Not               14
                               detected      detected       detected

As can be seen only few volatile chemical substances are liberated at 80 °C.
From previous studies it is known that carbon disulfide and dibutylamine are
degradation products from zinc dibutyldithiocarbamate and that both are
found in the rubber in spite of the low boiling point of carbondisulfide. BHT
is a frequently applied and relatively volatile anti-oxidant and 1,2-ethandiol
find use as a dispersing agent/ancillary substance. Hydrocarbons liberated
may originate from the applied colorants.




                                                                                       25
     There is a good matching between the results from degassing at 80 ºC and at
     150 ºC, as the relative amount of volatile chemical substances detected at the
     low temperature are reflected in the chromatograms (lower area counts).




26
7 Analysis for nitrosamines and
nitrosatable substances

Balloon nos. 3, 6, 16, and 20 were selected for analysis for nitrosamines and
nitrosatable substances according to DS/ EN 12 868, which as previously
mentioned is used by analysis of soothers and bottle teats. The selection is
made on basis of the TLC screenings and the extraction yields from
dichlormethane.

The standard lists 11 nitrosamines, which are causing health concerns in the
mentioned products. Below is a list of the nitrosamines found in the analysed
balloons with specification of concentrations. TIC is an abbreviation of total
ion current by the mass spectroscopic detection.

Table 7.1 Migration of selected nitrosamines - Balloon no. 3
                              CAS-no.       Content mg/kg       Detection limit
                                            (%RSD)              mg/kg
N-nitroso-dimethylamine       62-75-9       0.03* (10)          0.004
N-nitroso-ethylmethylamine    10595-95-6    -                   0.005
N-nitroso-diethylamine        55-18-5       -                   0.004
N-nitroso-dipropylamine       621-64-7      -                   0.005
N-nitroso-dibutylamine        89-16-3       0.08 (14)           0.004
N-nitroso-pyrrolidine         930-55-2      -                   0.007
N-nitroso-morpholine          59-89-2       -                   0.007
N-nitroso-piperidine          100-95-4      0.003**             0.002
N-nitroso-diphenylamine       86-30-6       -                   0.004
Total                                       0.08-0.11
* Maximum migration. Complete characterisation impossible due to coinciding
   peaks in TIC of extract..
** Maximum migration. Detected in only one of the two double determinations.

Table7.2 Migration of selected nitrosatable compounds - balloon no. 3
                            CAS-no.         Content mg/kg     Detection limit
                                            (%RSD)            mg/kg
N-nitroso-dimethylamine     62-75-9         2.8 (2)           0.004
N-nitroso-ethylmethylamine  10595-95-6      -                 0.005
N-nitroso-diethylamine      55-18-5         -                 0.004
N-nitroso-dipropylamine     621-64-7        -                 0.005
N-nitroso-dibutylamine      924-16-3        8.1 (25)          0.004
N-nitroso-pyrrolidine       930-55-2        -                 0.007
N-nitroso-morpholine        59-89-2         -                 0.007
N-nitroso-piperidine        100-95-4        0.01* (2)         0.002
N-nitroso-diphenylamine     86-30-6         -                 0.004
Total                                       10.9
*Maximum migration. Complete characterisation impossible due to coinciding peaks
in TIC of the extract.




                                                                                  27
     Table 7.3 Migration of selected nitrosamines – Balloon no. 6
                                   CAS-no.          Content mg/kg        Detection limit
                                                    (%RSD)               Mg/kg
     N-nitroso-dimethylamine       62-75-9          0.02* (2)            0.004
     N-nitroso-ethylmethylamine    10595-95-6       -                    0.005
     N-nitroso-diethylamine        55-18-5          -                    0.004
     N-nitroso-dipropylamine       621-64-7         -                    0.005
     N-nitroso-dibutylamine        924-16-3         0.006; 0.01**        0.004
     N-nitroso-pyrrolidine         930-55-2         -                    0.007
     N-nitroso-morpholine          59-89-2          -                    0.007
     N-nitroso-piperidine          100-95-4         -                    0.002
     N-nitroso-diphenylamine       86-30-6          -                    0.004
     Total                                          0-0.03
     * Maximum migration. Complete characterisation impossible due to coinciding
        peaks in TIC of extract.
     ** Maximum migration. Double determination differs more than 25%.

     Table 7.4 Migration of selected nitrosatable compounds - balloon no. 6
                                  CAS-no.         Content mg/kg      Detection limit
                                                  (%RSD)             Mg/kg
     N-nitroso-dimethylamine      62-75-9         2.7; 5.4 **        0.004
     N-nitroso-ethylmethylamine   10595-95-6      -                  0.005
     N-nitroso-diethylamine       55-18-5         -                  0.004
     N-nitroso-dipropylamine      621-64-7        -                  0.005
     N-nitroso-dibutylamine       924-16-3        0.08; 0.12 ***     0.004
     N-nitroso-pyrrolidine        930-55-2        -                  0.007
     N-nitroso-morpholine         59-89-2         -                  0.007
     N-nitroso-piperidine         100-95-4        -                  0.002
     N-nitroso-diphenylamine      86-30-6         -                  0.004
     Total                                        2.8-5.4
     * Maximum migration. Complete characterisation impossible due to coinciding
        peaks in TIC of extract.
     ** Maximum migration. Double determination differs more than 25%.
     *** Maximum migration. Double determination differs more than 25%.

     Table 7.5 Migration of selected nitrosamines - Balloon no. 16
                                  CAS-no.        Content mg/kg        Detection limit
                                                 (%RSD)               mg/kg
     N-nitroso-dimethylamine      62-75-9        0,02* (10)           0,004
     N-nitroso-ethylmethylamine   10595-95-6     -                    0,005
     N-nitroso-diethylamine       55-18-5        -                    0,004
     N-nitroso-dipropylamine      621-64-7       -                    0,005
     N-nitroso-dibutylamine       924-16-3       0,02; 0,03**         0,004
     N-nitroso-pyrrolidine        930-55-2       -                    0,007
     N-nitroso-morpholine         59-89-2        -                    0,007
     N-nitroso-piperidine         100-95-4       0,004* (0,5)         0,002
     N-nitroso-diphenylamine      86-30-6        0,006; 0,009 ***     0,004
     Total                                       0,03-0,04
     * Maximum migration. Complete characterisation impossible due to coinciding
        peaks TIC of extract.
     ** Maximum migration. Double determination differs more than 25%.
     *** Double determination differs more than 25%.




28
Table 7.6 Migration of selected nitrosatable compounds - balloon no. 16.
                             CAS-nr.        Content mg/kg      Detection limit
                                            (%RSD)             mg/kg
N-nitroso-dimethylamine      62-75-9        2.6 (13)           0.004
N-nitroso-ethylmethylamine   10595-95-6     -                  0.005
N-nitroso-diethylamine       55-18-5        -                  0.004
N-nitroso-dipropylamine      621-64-7       -                  0.005
N-nitroso-dibutylamine       924-16-3       8.0 (7)            0.004
N-nitroso-pyrrolidine        930-55-2       -                  0.007
N-nitroso-morpholine         59-89-2        -                  0.007
N-nitroso-piperidine         100-95-4       -                  0.002
N-nitroso-diphenylamine      86-30-6        -                  0.004
Total                                       10.6
* Maximum migration. Complete characterisation impossible due to coinciding
  peaks in TIC of extract.

Table 7.7 Migration of selected nitrosamines - Balloon no. 20
                             CAS-nr.        Content mg/kg        Detection limit
                                            (%RSD)               mg/kg
N-nitroso-dimethylamine      62-75-9        -                    0.004
N-nitroso-ethylmethylamine   10595-95-6     -                    0.005
N-nitroso-diethylamine       55-18-5        -                    0.004
N-nitroso-dipropylamine      621-64-7       -                    0.005
N-nitroso-dibutylamine       924-16-3       -                    0.004
N-nitroso-pyrrolidine        930-55-2       -                    0.007
N-nitroso-morpholine         59-89-2        -                    0.007
N-nitroso-piperidine         100-95-4       -                    0.002
N-nitroso-diphenylamine      86-30-6        -                    0.004
Total                                       -

Table 7.8 Migration of selected nitrosatable compounds - balloon no. 20
                             CAS-nr.          Content mg/kg      Detection limit
                                              (%RSD)             mg/kg
N-nitroso-dimethylamine      62-75-9          0,6 ; 1,3 **       0,004
N-nitroso-ethylmethylamine   10595-95-6       -                  0,005
N-nitroso-diethylamine       55-18-5          -                  0,004
N-nitroso-dipropylamine      621-64-7         -                  0,005
N-nitroso-dibutylamine       924-16-3         0,2* (20)          0,004
N-nitroso-pyrrolidine        930-55-2         -                  0,007
N-nitroso-morpholine         59-89-2          -                  0,007
N-nitroso-piperidine         100-95-4         -                  0,002
N-nitroso-diphenylamine      86-30-6          -                  0,004
Total                                         0,6-1,5
* Maximum migration. Complete characterisation impossible due to coinciding
  peaks in TIC of extract.

Not unexpectedly N-nitrosodibutylamine and N-nitrosodimethylamine are
the present nitrosamine types and the nitrosatable substances are likewise
dominated by dibutylamine and dimethylamine.

A comparison of the results with the regulations on soothers and bottle teats
shows that the balloons are violating these requirements significantly.
Conversion of the total migration of nitrosamines and nitrosatable substances
to µg/kg gives the grand totals stated in the table.

Table 7.9 Survey of total migration of nitrosamines and nitrosatable compounds in
the selected balloons
Chemical class Balloon no. 3        Balloon no. 6    Balloon no. 16 Balloon no. 20
                  µg/kg             µg/kg            µg/kg            µg/kg
Nitrosamines      80-110            0-30             30-40            <7
Nitrosatable      10,900            2,800-5,400      10,600           600-1,500
compounds




                                                                                   29
     Table 7.9 shows that balloon no. 20 as to the nitrosamine complies with the
     requirement to soothers and bottle teats. This may also be the case for sample
     no. 6. Balloons nos. 3 and 16 exceed the limit value of 10 µg/kg for soothers
     and bottle teats. All four samples comply with the German regulations on
     balloons, i.e. a maximum content of 200 µg/kg (0.2 mg/kg). Balloons nos. 3, 6
     and 6 do not fulfill the requirements to neither the maximum content of
     nitrosatable substances according to the limit values for soothers and bottle
     teats of 100 µg/kg nor the German requirements to 2,000 µg/kg (2 mg/kg).

     At the same time it is assessed that the analysis method does not provide a
     correct value of the nitrosatable compounds at concentrations as high as they
     occur in balloons nos. 3 and 6, because of insufficient time for nitrosation of
     the amines. It can be seen that dibutylamine is still present in the
     chromatogram, although it is nitrosatable.

     It should be mentioned that N-nitroso-diphenylamine, which has been
     detected in balloon no. 6, is used as retarder by vulcanisation of rubber
     (reducing the reaction velocity), but it is not likely that it is used by
     production of rubber products in Europe due to its harmful properties (Xn
     R22, R43, R51/53, S24, S36, S60, S61).

     N-nitroso-piperidine may originate from the use of piperidine pentamethylene
     dithiocarbamate which will liberate piperidine at the vulcanisation
     temperature.




30
8 Analysis for bioavailable heavy
metals

The analysis results of the three balloon types selected for determination of
release of heavy metals according to DS/EN 71-3, appear from Table 8.1.

Table 8.1 Bioavailable heavy metal according to DS/EN 71-3
Lab. mark.          R32960-5          R32960-10        R32960-12
Sample mark.        Balloon no. 10    Balloon no. 16   Balloon no. 20
Element                                                                     Detection
                                                                            limit
Sb mg/kg           -                  -                  -                  6
As mg/kg           -                  -                  -                  2,5
Ba mg/kg           -                  -                  -                  25
Cd mg/kg           -                  -                  -                  5
Cr mg/kg           -                  -                  -                  2,5
Pb mg/kg           -                  -                  -                  9
Hg mg/kg           -                  -                  -                  2,5
Se mg/kg           -                  -                  -                  50
Ni mg/kg           -                  -                  -                  2
”-” less than the detection limit, which is 1/10 of the requirement value in the
standard

Ni is not comprised by the standard but is included in the analysis.

As can be seen from Table 8.1, bio available heavy metals have not been
detected in the analysed balloons, which means that no heavy metal-based
accelerators (e.g. nickel dithiocarbamate salts) nor colorants have been used
in the manufacture of the balloons.




                                                                                        31
32
9 Conclusion in short


It was established that several of the 20 different types of balloons purchased
at retailers did not comply with the requirements to labelling. Some of the
examples had a CE-label, although the requirements to the labelling according
to EN 71 ”Safety of Toys” was not complied with.

Three different balloon types in the colours yellow, red, or orange, which were
analysed for release of heavy metals according to EN 71-3, did not liberate
measurable amounts to the contact liquid at a detection limit which was ten
times lower than the requirement values.

Analyses for content of nitrosamines and nitrosatable chemical substances
according to EN 12868 showed that none of the balloon samples were
complying with the requirement to limit values for soothers and bottle teats.

However, the four analysed balloons complied with the German regulations
(”Bewertung von Nitrosaminen in Luftballons” , Ergänzende Stellungsnahme
des BfR vom 26. März) of 0.2 mg/kg for nitrosamines.

The limit value for nitrosatable substances is 2 mg /kg.

Only one of the analysed balloon types complied with the limit value for
nitrosatable substances. All others did not meet the requirements.

The balloon type which complied with both requirements was according to
the packaging certified by TÜV.

The chapter ”Summary and Conclusion” documents the analysis results in
more detail.




                                                                                33
34
10 References

 1. Asian dipped Goods handbook and directory 2004, John S. Powath,
    Rubber Asia, 1.udgave 2004
 2. Migration of nitrosamines from rubber products - are balloons and
    condoms harmful to the human health? Werner Altkofer et al. Mol.
    Nutr. Food Res. 2005, 49
 3. Study on the Impact of the Revision of the Counsil Directive
    88/378/EEC on the Safety of Toys, Final Report RPA Oktober 2004
 4. Kunststoffe im Lebensmittelverkehr – 57. lfg. Oktober 2005,
    Bundesinstitut für Risikobewertung (BfR), Bevertung von
    Nitrosaminen in Luftballons




                                                                    35

								
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